Refractory product having improved flow

ABSTRACT

An unshaped product including a particulate mixture containing: a coarse fraction, representing &gt;50%&lt;91% of particulate mixture, in mass percentage, and containing particles size ≧50 μm, “coarse particles”, and matrix fraction, forming remainder up to 100% of particulate mixture, and containing particles sizes &lt;50 μm, product having chemical analysis, in mass percentage based on oxides of product, such: −45%&lt;Al 2 O 3 , −7.5%&lt;SiO 2 &lt;35%, −0%≦ZrO 2 &lt;33%, providing 10%&lt;SiO2+ZrO2&lt;54%, −0.15%&lt;B 2 O 3 &lt;8%, other oxides: &lt;6%, Al 2 O 3  forming remainder up to 100%, coarse fraction including more than 15% coarse particles having size &gt;1 mm, in mass percentage based on particulate mixture, matrix fraction having a chemical analysis, in mass percentage based on oxides of matrix fraction, such: Al 2 O 3 +SiO 2 +ZrO 2 &gt;86%, providing 35%&lt;Al 2 O 3 .

TECHNICAL FIELD

The invention relates to an unshaped product intended for the manufacture of a sintered refractory product, in particular intended for a glass furnace crown, and to such a sintered refractory product.

PRIOR ART

The sintered refractory products used in glass melting furnace crowns, and in particular mullite-based products, are known for their good creep resistance at high temperatures, in particular at temperatures above 1400° C.

An increase in the sizes of furnaces and/or more severe conditions of use, and in particular an increase in melting temperatures, require the use of products that are ever more resistant to creep.

One aim of the invention is to at least partially meet this need.

SUMMARY OF THE INVENTION

The invention provides an unshaped product comprising a particulate mixture consisting of:

-   -   a coarse fraction, representing more than 50% and less than 91%         of the particulate mixture, as weight percentage, and consisting         of the particles of the unshaped product having a size greater         than or equal to 50 μm, referred to as “coarse particles”, and     -   a matrix fraction, forming the remainder up to 100% of the         particulate mixture, and consisting of the particles of the         unshaped product having a size less than 50 μm, referred to as         “matrix particles”,         the unshaped product having a chemical analysis, as weight         percentages on the basis of the oxides of the unshaped product,         such that:     -   45%<Al₂O₃₁     -   7.5%<SiO₂<35%,     -   0%≦ZrO₂<33%, provided that 10%<SiO₂+ZrO₂<54%,     -   0.15%<B₂O₃<8%,     -   other oxides: <6%,         Al₂O₃ constituting the remainder up to 100%,         said coarse fraction comprising more than 15% of coarse         particles having a size greater than 1 mm, as weight percentage         on the basis of the particulate mixture,         said matrix fraction having a chemical analysis, as weight         percentages on the basis of the oxides of the matrix fraction,         such that:     -   Al₂O₃+SiO₂+ZrO₂>86%, provided that 35%<Al₂O₃.

As will be seen in greater detail in the remainder of the description, an unshaped product according to the invention makes it possible to manufacture a sintered product that is particularly resistant to creep and perfectly suitable for use in a crown of a glass furnace.

Preferably, an unshaped product according to the invention further comprises one, and preferably several, of the following optional characteristics:

-   -   in the unshaped product, the content of “other oxides” is         preferably less than 5%, preferably less than 4%, preferably         less than 3%, preferably less than 2% or even less than 1%. In         one embodiment, the “other oxides” are impurities;     -   the matrix fraction, other than (optional) particles comprising         boron, preferably consists, for more than 80%, more than 90%,         more than 95%, or even approximately 100% of its weight, of         alumina particles and/or silica particles and/or mullite         particles and/or mullite-zirconia particles and/or particles of         a silicoaluminous material having an alumina content greater         than 50%, preferably chosen from purusite, kerphalite, cyanite,         andalousite, sillimanite, a chamotte and mixtures thereof.         Preferably, the matrix fraction consists of alumina particles         and/or silica particles and/or mullite particles. More         preferably, the matrix fraction consists of alumina particles         and silica particles, and/or of mullite particles;     -   if the silica content in the matrix fraction is greater than 10%         as weight percentage on the basis of the oxide phases of the         matrix fraction, said matrix fraction has an alumina/silica         weight ratio or “A/S ratio” greater than 2, or even greater than         2.5, or even greater than 3, and/or less than 10, preferably         less than 9, preferably less than 8, preferably less than 7,         preferably less than 6, preferably less than 5, or even less         than 4;     -   the unshaped product comprises less than 10%, less than 5%, less         than 1% of silicon carbide, preferably no silicon carbide, as         weight percentage on the basis of the unshaped product;     -   the sintered product comprises less than 10%, less than 5%, less         than 1% of aluminum metal, as weight percentage on the basis of         the unshaped product, and preferably does not comprise aluminum         metal;     -   the oxides represent more than 70%, preferably more than 80%,         preferably more than 85%, preferably more than 90%, preferably         more than 95%, preferably more than 96%, preferably more than         97%, more preferably more than 98% of the weight of the unshaped         product;     -   the unshaped product preferably comprises more than 20%,         preferably more than 25% of coarse particles having a size         greater than 1 mm, as weight percentage;     -   the coarse fraction preferably consists, for more than 80%, more         than 90%, more than 95%, or even approximately 100% of its         weight, of alumina particles and/or mullite particles and/or         mullite-zirconia particles and/or particles of a silicoaluminous         material having an alumina content greater than 50%, preferably         chosen from purusite, kerphalite, cyanite, andalousite,         sillimanite, a chamotte and mixtures thereof. Preferably, the         coarse fraction consists, for more than 80%, more than 90%, more         than 95%, or even approximately 100% of its weight, of alumina         particles and/or mullite particles and/or mullite-zirconia         particles;     -   the coarse particles having a size greater than 1 mm are chosen         from coarse particles of mullite and/or coarse particles of         mullite-zirconia and/or coarse particles of alumina and/or         coarse particles of a silicoaluminous material having an alumina         content greater than 50%, preferably chosen from purusite,         kerphalite, cyanite, andalousite, sillimanite, a chamotte and         mixtures thereof;     -   preferably, the coarse fraction consists of mullite particles;     -   preferably, more than 80%, preferably more than 90% by weight of         the coarse particles have a size greater than 200 μm, preferably         greater than 300 μm, preferably greater than 400 μm, or even         greater than 0.5 mm and/or less than 25 mm, preferably less than         or equal to 15 mm, preferably less than or equal to 10 mm, or         even less than or equal to 5 mm;     -   the amount of boron, expressed in the form B₂O₃, is greater than         0.2%, preferably greater than 0.25%, preferably greater than         0.5%, preferably greater than 0.75%, or even greater than 0.9%,         and/or less than 6.5%, preferably less than 5.8%, preferably         less than 5.5%, preferably less than 5.2%, preferably less than         4.8%, preferably less than 4.5%, preferably less than 4.2%,         preferably less than 3.9%, preferably less than 3.5%, preferably         less than 3.2%, preferably less than 2.9%, preferably less than         2.6%;     -   the boron is provided by a boron compound chosen from boron         carbide, boron oxides, boric acid, colemanite, sodium borate,         compounds comprising silica and boron oxide, for instance         danburite or ulerite, SiB₆, alumina borates, AlB₃ and mixtures         thereof. Preferably, the boron compound is chosen from boron         carbide, boron oxide, H₃BO₃ and mixtures thereof. Preferably,         the boron compound is boron carbide;     -   preferably, more than 50%, preferably more than 60%, preferably         more than 70%, preferably more than 80%, or even more than 90%,         or even approximately 100% of the particles comprising boron are         matrix particles, as weight percentage on the basis of the         oxides;     -   the Al₂O₃ content of the matrix fraction, as weight percentages         on the basis of the oxides of the matrix fraction, is less than         90%;     -   the unshaped product comprises a forming additive and/or a         solvent, preferably water.

The invention also relates to a process for manufacturing a sintered part, comprising the following steps:

-   -   A) preparation of a starting charge from an unshaped product         according to the invention;     -   B) forming of said starting charge so as to form a preform;     -   C) sintering of said preform.

The sintering temperature is preferably greater than or equal to 1300° C., preferably greater than or equal to 1350° C., preferably greater than 1400° C., preferably greater than 1500° C. and/or less than or equal to 1850° C., preferably less than 1800° C., more preferably less than or equal to 1750° C.

The invention also relates to a starting charge obtained at the end of step A), which is a particular case of an unshaped product according to the invention, and a preform obtained at the end of step B).

The invention also relates to a sintered product obtained from an unshaped product according to the invention, in particular according to a process according to the invention.

The invention thus relates to a sintered product having a microstructure consisting of grains bonded by a matrix, and having a chemical analysis such that, as weight percentages on the basis of the oxides and for a total of 100%:

-   -   45%<Al₂O₃,     -   7.5%<SiO₂<37%,     -   0%≦ZrO₂<35%, provided that 10%<SiO₂+ZrO₂<54.3%,     -   0.1%<B₂O₃<2.5%,     -   other oxides: <6.4%,         Al₂O₃ constituting the remainder up to 100%,         the boron being distributed in the body of the sintered product,         preferably in the matrix, preferably substantially         homogeneously, and         more than 15% of grains having an equivalent diameter greater         than 1 mm.

Preferably, a sintered product according to the invention further comprises one, and preferably several, of the following optional characteristics:

-   -   the sintered product has the shape of a block of which all the         dimensions are greater than 1 mm, greater than 5 mm, greater         than 5 cm and of which all the dimensions are preferably less         than 150 cm, or even less than 100 cm, or even less than 60 cm;     -   the sintered product has a weight greater than 1 kg, greater         than 5 kg, or even greater than 10 kg;     -   the sintered product preferably has an apparent density greater         than 2.3 g/cm³, preferably greater than 2.5 g/cm³, and/or less         than 3.5 g/cm³, preferably less than 3.2 g/cm³;     -   the amount of boron, expressed in the form B₂O₃, is greater than         0.15%, preferably greater than 0.2%, preferably greater than         0.25%, preferably greater than 0.3%, preferably greater than         0.4%, preferably greater than 0.5%, and/or less than 2%,         preferably less than 1.5%, preferably less than 1%, preferably         less than 0.8%;     -   the content of “other oxides” is preferably less than 6%,         preferably less than 5%, preferably less than 4%, preferably         less than 3%, preferably less than 2%, or even less than 1%. In         one embodiment, the “other oxides” are impurities;     -   the sintered product preferably comprises more than 17%,         preferably more than 23%, preferably more than 28% of grains         having an equivalent diameter greater than 1 mm;     -   the aggregate preferably consists, for more than 80%, more than         90%, more than 95%, or even approximately 100% by number, of         alumina grains and/or mullite grains and/or mullite-zirconia         grains;     -   the grains having an equivalent diameter greater than 1 mm are         chosen from mullite grains and/or mullite-zirconia grains and/or         alumina grains;     -   preferably, the aggregate consists of mullite grains.

Finally, the invention relates to a furnace, in particular a glass furnace, and in particular a glass melting zone or a glass refining zone or a molten glass feeder, comprising a sintered product according to the invention, in particular in a region which is not in contact with a molten material, and in particular which is not in contact with molten glass, preferably in a superstructure (comprising a crown and walls supporting said crown), more preferably in a crown.

An unshaped product, respectively a sintered product, according to the invention may further comprise one or more (if they are technically compatible) of the following optional characteristics:

-   -   preferably, more than 50%, preferably more than 60%, preferably         more than 70%, preferably more than 80%, or even more than 90%,         or even approximately 100% of the boron is in matrix particles,         respectively in the matrix;     -   SiO₂+ZrO₂>15%, preferably SiO₂+ZrO₂>16%, preferably         SiO₂+ZrO₂>20% and/or SiO₂+ZrO₂<50%, preferably SiO₂+ZrO₂<46%,         preferably SiO₂+ZrO₂<40%;     -   SiO₂>10%, preferably SiO₂>13% and/or SiO₂<30%, preferably         SiO₂<27%;     -   in one embodiment, ZrO₂<4%, preferably ZrO₂<3%, preferably         ZrO₂<2%, preferably ZrO₂<1%, preferably ZrO₂<0.5%, or even         ZrO₂<0.2%, or even the ZrO₂ content is approximately zero;     -   in one embodiment, ZrO₂>8.5%, preferably ZrO₂>15.5%, or even         ZrO₂>22.8% and/or ZrO₂<33%;     -   Al₂O₃+SiO₂+ZrO₂>92%, preferably Al₂O₃+SiO₂+ZrO₂>94%, preferably         Al₂O₃+SiO₂+ZrO₂>96%, or Al₂O₃+SiO₂>83%, preferably         Al₂O₃+SiO₂>85%, preferably Al₂O₃+SiO₂>90%, preferably         Al₂O₃+SiO₂>92%, preferably Al₂O₃+SiO₂>94%, preferably         Al₂O₃+SiO₂>96%;     -   the unshaped product and/or the matrix fraction, respectively         the sintered product and/or the matrix, has (have)         -   a content of Al₂O₃+SiO₂ greater than 85%, or even greater             than 90%, or even greater than 92%, or even greater than             94%, or even greater than 96%; or         -   a content of Al₂O₃+SiO₂+ZrO₂ greater than 85%, or even             greater than 90%, or even greater than 92%, or even greater             than 94%, or even greater than 96%;     -   the unshaped product and/or the matrix fraction, respectively         the sintered product and/or the matrix, has (have) a content of         Al₂O₃+SiO₂+ZrO₂+B₂O₃ greater than 94.5%, preferably greater than         95%, preferably greater than 98%, or even greater than 99%;     -   the Al₂O₃ content in the unshaped product and/or the matrix         fraction, respectively the sintered product and/or the matrix,         is preferably greater than 45%, or even greater than 50%, or         even greater than 55%, or even greater than 60% and/or         preferably less than 89%, preferably less than 85%, preferably         less than 80%;     -   in one embodiment, the ZrO₂ content in the unshaped product         and/or the matrix fraction, respectively the sintered product         and/or the matrix, is preferably less than 4%, preferably less         than 3%, preferably less than 2%, preferably less than 1%,         preferably less than 0.5%, or even less than 0.2%, or even         approximately zero;     -   the matrix fraction, respectively the matrix, represents more         than 15%, preferably more than 20%, or even more than 25% and/or         less than 40%, or even less than 35%, or even less than 30% of         the weight of the particulate mixture of the unshaped product,         respectively of the sintered product;     -   the oxides represent more than 90%, preferably more than 95%, or         even approximately 100% of the weight of the unshaped product         and/or of the matrix fraction and/or of the coarse fraction,         respectively of the sintered product and/or of the matrix and/or         of the aggregate;     -   the coarse particles, respectively the grains, and/or the matrix         particles are sintered or molten, preferably molten.

In a first preferred particular embodiment, in the unshaped product or the sintered product:

-   -   the content of Al₂O₃+SiO₂ is preferably greater than 83%,         preferably greater than 85%, preferably greater than 90%,         preferably greater than 92%, preferably greater than 94%,         preferably than 96% and/or     -   the ZrO₂ content is preferably less than 4%, preferably less         than 3%, preferably less than 2%, preferably less than 1%,         preferably less than 0.5% and/or     -   the SiO₂ content is preferably greater than 10%, greater than         15%, or even greater than 20% and/or less than 30%, preferably         less than 27%.

Preferably, the unshaped product has:

-   -   a chemical analysis such that, as weight percentages on the         basis of the oxides:         -   Al₂O₃: remainder up to 100%, and         -   SiO₂: 21%-25%, and         -   ZrO₂<1%, preferably ZrO₂<0.5%, and         -   0.2%<B₂O₃<5.2%, preferably B₂O₃<4.5%, preferably B₂O₃<3.5%,             preferably B₂O₃<2.9%, preferably B₂O₃<2.6%, and         -   other oxides: <3%, preferably <2%, preferably <1%, and     -   an amount of matrix particles of between 20% and 35% of the         weight of the particulate mixture of the unshaped product, and a         matrix fraction having a chemical analysis such that         Al₂O₃+SiO₂+ZrO₂+B₂O₃>90%, preferably Al₂O₃+SiO₂+B₂O₃>90% as         weight percentages on the basis of the oxides of the matrix         fraction, and     -   more than 15%, preferably more than 20%, preferably more than         25% of coarse particles having a size greater than 1 mm.

Preferably, the unshaped product has a matrix fraction comprising an amount of silica of between 10% and 30%, as weight percentages on the basis of the oxides of the matrix fraction, and an alumina/silica ratio of between 2 and 5.

Preferably, the mullite represents more than 50%, preferably more than 60%, preferably more than 70%, preferably more than 75% of the weight of the crystalline phases of the unshaped product, and more preferably Al₂O₃≧71% and/or Al₂O_(3≦)79%.

Preferably, the sintered product has:

-   -   a chemical analysis such that, as weight percentages on the         basis of the oxides:         -   Al₂O₃: remainder up to 100%, and         -   SiO₂: 21%-25%, and         -   ZrO₂<1%, preferably ZrO₂<0.5%, and         -   B₂O₃>0.2%, preferably B₂O₃>0.25%, preferably B₂O₃>0.3%,             preferably B₂O₃>0.4%, preferably B₂O₃>0.5% and B₂O₃<1.5%,             preferably B₂O₃<1%, preferably B₂O₃<0.8%, and         -   other oxides: <3%, preferably <2%, preferably <1%, and     -   more than 15%, preferably more than 17%, preferably more than         23%, preferably more than 28% of grains having an equivalent         diameter greater than 1 mm.

Preferably, the matrix of the sintered product has a chemical analysis such that Al₂O₃+SiO₂+B₂O₃>90%, as weight percentage on the basis of the oxides of the matrix of the sintered product.

Preferably, the mullite represents more than 50%, preferably more than 60%, preferably more than 70%, preferably more than 75% of the weight of the crystalline phases of the sintered product, and more preferably Al₂O₃≧71% and/or Al₂O₃≦79%.

In a second preferred particular embodiment, in the unshaped product or the sintered product,

-   -   the content of Al₂O₃+ZrO₂+SiO₂ is preferably greater than 87%,         preferably greater than 90%, preferably greater than 92%,         preferably greater than 94%, preferably greater than 96% and/or     -   the SiO₂ content is preferably greater than 7.5%, greater than         10.5%, or even greater than 13% and/or less than 20%, preferably         less than 18% and/or     -   the ZrO₂ content is preferably greater than 8.5%, greater than         15.5%, or even greater than 22.8% and/or less than 33%.

Preferably, the unshaped product has:

-   -   a chemical analysis such that, as weight percentages on the         basis of the oxides,         -   Al₂O₃: remainder up to 100%, and         -   SiO₂: 14%-17%, and         -   ZrO₂: 26%-32%, and         -   0.2%<B₂O₃<5.2%, preferably B₂O₃<4.5%, preferably B₂O₃<3.5%,             preferably B₂O₃<2.9%, preferably B₂O₃<2.6%, and         -   other oxides: <3%, preferably <2%, preferably <1%, and     -   an amount of matrix particles of between 20% and 35% of the         weight of the particulate mixture of the unshaped product, and a         matrix fraction having a chemical analysis such that         Al₂O₃+SiO₂+ZrO₂+B₂O₃>90%, preferably Al₂O₃+SiO₂+ZrO₂+B₂O₃>94%,         and     -   more than 10%, preferably more than 15%, preferably more than         20%, preferably more than 25% of coarse particles having a size         greater than 1 mm.

Preferably, the unshaped product has a matrix fraction comprising an amount of silica of between 10% and 30%, as weight percentages on the basis of the oxides of the matrix fraction, and an alumina/silica ratio of between 2 and 5.

Preferably, the mullite represents more than 30%, preferably more than 36%, preferably more than 42%, preferably more than 45% of the weight of the crystalline phases of the unshaped product, and more preferably Al₂O₃≧44% and/or Al₂O₃≦50%.

Preferably, the sintered product has:

-   -   a chemical analysis such that, as weight percentages on the         basis of the oxides,         -   Al₂O₃: remainder up to 100%, and         -   SiO₂: 14%-17%, and         -   ZrO₂: 26%-32%, and         -   B₂O₃>0.2%, preferably B₂O₃>0.25%, preferably         -   B₂O₃>0.3%, preferably B₂O₃>0.4%, preferably B₂O₃>0.5% and             B₂O₃<1.5%, preferably B₂O₃<1%, preferably B₂O₃<0.8%, and         -   other oxides: <3%, preferably <2%, preferably <1%, and     -   more than 15%, preferably more than 17%, preferably more than         23%, preferably more than 28% of grains having an equivalent         diameter greater than 1 mm, as surface percentage measured on         images of polished surfaces.

Preferably, the matrix of the sintered product has a chemical analysis such that Al₂O₃+SiO₂+ZrO₂+B₂O₃>90%, as weight percentage on the basis of the oxides of the matrix of the sintered product.

Preferably, the mullite represents more than 30%, preferably more than 36%, preferably more than 42%, preferably more than 45% of the weight of the crystalline phases of the sintered product, and more preferably Al₂O₃≧44% and/or Al₂O₃≦50%.

DEFINITIONS

-   -   An unshaped product is a product which does not have a solid         structure, or “monolithic” structure. A powder or a slip are         examples of unshaped products.     -   A powder or a particulate mixture are dry assemblies of         particles not bonded to one another. The percentages relating to         a particulate mixture or to a powder are therefore implicitly on         the basis of the dry solids.     -   A powder differs from a particulate mixture in that the         particles all necessarily have substantially the same         composition. The term “powder” is in particular conventionally         used to denote the raw materials.     -   The term “particle” is intended to mean a solid object of which         the size is less than 30 mm. Particles having a size greater         than or equal to 50 μm, referred to as “coarse particles”, and         those having a size less than 50 μm, referred to as “matrix         particles” are in particular distinguished. All of the coarse         particles constitute the “coarse fraction”. All of the matrix         particles constitute the “matrix fraction”.     -   The size of the particles of a powder or of a particulate         assembly is conventionally evaluated by a particle size         distribution characterization carried out with a laser particle         size analyzer for particles having a size less than 2 mm and by         sieving using sieves with square meshes having an opening         greater than 2 mm for particles having a size greater than 2 mm.         The laser particle size analyzer may be, for example, a Partica         LA-950 from the company Horiba. The coarse particles         substantially retain their dimensions and their morphology         during sintering and therefore substantially correspond to the         grains of the sintered product.     -   The equivalent diameter of a grain measured on an image of a         polished surface is the diameter of the circle having the same         area as said grain. The equivalent diameter may be evaluated         using image processing software.     -   The percentage of grains having an equivalent diameter greater         than “n” mm, for example 1 mm, is the percentage of the area of         a polished surface of a product occupied by grains having an         equivalent diameter greater than “n” mm.     -   The percentiles or “centiles” 10 (A₁₀), 50 (A₅₀), 90 (A₉₀) and         99.5 (A_(99.5)), and more generally “n” A_(n) of a property A of         a population, for example of a population of particles, are the         values of this property corresponding to the percentages of 10%,         50%, 90%, 99.5% and n %, respectively, on the cumulative         distribution curve relative to this property, the values         relating to this property being classified in increasing order.         In particular, the percentiles D_(n) relate to sizes of         particles of a powder or of a particulate assembly. The         percentages are by weight.     -   For example, 10% by weight of the particles of the powder have a         size less than D₁₀ and 90% of the particles by weight have a         size greater than or equal to D₁₀. The percentiles relating to         the particle size may be determined by means of a particle size         distribution performed using a laser particle size analyzer         and/or sieving.     -   The 50 percentile is conventionally referred to as the “median”         percentile. For example, the D₅₀ percentile is conventionally         referred to as “median size”.     -   The term “sintering” refers to the consolidation by heat         treatment at more than 1100° C. of a preform, with optionally         partial or total melting of some of its constituents (but not of         all of its constituents, such that the preform is not converted         into a liquid mass).     -   Generally, the sintering results in the conversion of the matrix         fraction into a bonding phase, or “matrix”, which will bond the         coarse particles (substantially unaffected by the sintering) to         one another. In the interests of clarity, the term “grains”         refers to the coarse particles bonded by the matrix. The         assembly of grains is referred to as “aggregate”.     -   The term “impurities” is intended to mean the unavoidable         constituents unintentionally and necessarily introduced with the         raw materials or resulting from reactions with these         constituents. The impurities are not required constituents, but         merely tolerated constituents.     -   Unless otherwise indicated, all the percentages relating to         contents are weight percentages on the basis of the oxides, as         is conventional in refractory products. The weight content of a         constituent is conventionally expressed in the form of the most         stable oxide. Conventionally, the content of boron and of         elements of which the amount does not exceed 0.5% is determined         by “Inductively Coupled Plasma” or ICP, and in order to         determine the content of the other elements, a bead of the         product to be analyzed is produced by melting the product, then         the chemical analysis is carried out by X-ray fluorescence. The         machines conventionally used automatically convert the contents         of the non-oxide constituents into equivalent oxide contents.         Whatever the measuring method, the residual carbon and hydrogen         are not however quantitatively determined.     -   In the interests of clarity, the chemical formulae of the oxides         are used to exclusively denote the contents of these oxides in a         composition. For example, “B₂O₃”, “ZrO₂”, “HfO₂”, “SiO₂” or         “Al₂O₃” denote the contents of these oxides in the composition         and “boron oxide”, “zirconia”, “hafnia”, “silica” and “alumina”         are exclusively used to denote crystalline phases of these         oxides consisting of B₂O₃, ZrO₂, HfO₂, SiO₂ and Al₂O₃,         respectively. These oxides may however also be present in other         phases, in particular in the form of mullite or of         mullite-zirconia.     -   The term “mullite-zirconia particle” is intended to mean a         refractory particle obtained by sintering or by melting, and the         chemical analysis of which reveals the major presence of alumina         (Al₂O₃), of silica (SiO₂) and of zirconia (ZrO₂); the silica and         the alumina being present essentially in the form 2SiO₂-3Al₂O₃         (mullite).     -   The term “containing a” or “comprising a” is intended to mean         “comprising at least one”, unless otherwise indicated.     -   The various characteristics of a product according to the         invention may be determined by the characterization methods used         for the examples below.

BRIEF DESCRIPTION OF THE FIGURES

Other characteristics and advantages of the invention will further emerge on examining the drawing, provided by way of nonlimiting illustration, in which FIG. 1 diagrammatically represents a device that can be used to measure the creep resistance, and FIG. 2 diagrammatically represents the deformation of the small bar after a creep test.

DETAILED DESCRIPTION

An unshaped product according to the invention may be advantageously used for producing a sintered product having an aggregate bonded by a bonding matrix. To this effect, a process comprising steps A) to C) described above may be carried out.

In step A), a particulate mixture is mixed in a solvent, conventionally water. The sources of raw materials are determined according to the composition and the particle size distribution that are desired.

The Andréasen or Fuller-Bolomey compaction models may be used to adapt the particle size distribution to the apparent density desired for the sintered products. Such compaction models are in particular described in the work entitled “Traité de céramique et matériaux minéraux” [Treatise on ceramics and mineral materials], C. A. Jouenne, Editions Septima. Paris (1984), pages 403 to 405. In particular, this adaptation advantageously makes it possible to produce a sintered refractory product having an apparent density of between 2.3 g/cm³ and 3.5 g/cm³, preferably of between 2.5 g/cm³ and 3.2 g/cm³.

The boron compound may be added in solid form, for example in the form of a powder, and/or in liquid form, for example diluted in water. The boron may for example be provided in the form of a B₄C powder.

In one advantageous embodiment, the boron is provided in liquid form, preferably during the preparation of the starting charge, preferably at the time the mixture is prepared in step A), for example by dissolving and/or sprinkling. Advantageously, the boron compound is well dispersed in the starting charge.

Preferably, the starting charge contains a forming additive, preferably introduced in a dry form, preferably in an amount greater than 0.1% and less than 7%, preferably less than 5%, preferably less than 3%, or even less than 2%, as weight percentage on the basis of the weight of the particulate mixture.

The forming additive may in particular be chosen from the group consisting of:

-   -   clays;     -   plasticizers, for instance polyethylene glycol (or “PEG”) or         polyvinyl alcohol (or “PVA”);     -   cements, preferably with a high alumina content;     -   hydratable aluminas, for instance boehmite;     -   phosphates, preferably alumina phosphates;     -   sodium and/or potassium silicates;     -   geopolymers;     -   binders, including organic temporary binders such as organic         resins, lignosulfonates, carboxymethylcellu-lose, dextrin and         alginates;     -   deflocculants, such as alkali metal polyphosphates, alkali metal         polyacrylates, or polycarboxylates;     -   mixtures of these products.

Preferably, the forming additive is chosen from the group consisting of cements, deflocculants, clays, lignosulfonates, PVA and mixtures thereof.

When the boron or the additive is provided in the form of particles, these particles are of course part of the particulate mixture.

The unshaped product may be provided ready-to-use. Preferably, it is dry and contains the forming additive. It is then sufficient to mix it with a solvent, preferably water, in order to prepare the starting charge.

The amount of solvent depends on the technology used in step B).

In the case of forming by cold pressing, addition of an amount of water of between 1.5% and 4%, as weight percentage on the basis of the particulate mixture, is preferred. In the case of forming involving hydraulic bonding, for example pouring, addition of an amount of water of between 3% and 7%, as weight percentage on the basis of the particulate mixture, is preferred.

In step B), the starting charge may be poured into a mold, in order to be formed and converted into a preform according to conventional techniques, for example by pressing.

After step B) and before step C), the preform may undergo a drying step, in order to remove a part of the water having been used for the forming. Such a step is perfectly known to those skilled in the art.

In step C), the sintering conditions, and in particular the sintering temperature, depend on the composition of the preform. Those skilled in the art may readily control the quality of the sintering and optionally adjust the temperature accordingly. Usually, a sintering temperature of between 1350° C. and 1850° C., preferably of between 1500° C. and 1750° C., is very suitable. The sintering may be carried out in situ, i.e. after the preform has been placed in its working position, in particular in a crown of a glass furnace.

At the end of step C), a sintered refractory product according to the invention, having a substantially homogeneous distribution of the boron element, preferably in the matrix of said refractory product, is obtained.

The properties of this sintered product make it particularly well suited to use in a glass furnace, in particular in a glass furnace crown.

Examples

The following examples are given for illustrative purposes and do not limit the invention.

The content of boron and of elements of which the amount does not exceed 0.5% is determined by “Inductively Coupled Plasma” or ICP.

The content of other elements is determined by X-ray fluorescence.

The creep resistance is determined by means of the following method: a small bar 2 of the product to be tested, having a length equal to 200 mm, a width equal to 25 mm and a height equal to 15 mm, is placed on blocks 10 made of dense sintered alumina, said blocks being placed at each of the ends of the small bar such that the scope (in other words the length of the small bar not supported between the blocks) is equal to x=180 mm. A refractory brick 12 having a weight equal to 2670 g is placed at the center of the small bar on blocks 14 made of dense sintered alumina, separated from one another by y=40 mm, said brick having a length approximately equal to 110 mm, a width approximately equal to 75 mm and a height approximately equal to 200 mm (see FIG. 1). The center of the brick is approximately aligned with the center of the small bar to be tested. This assembly is then placed in an electric furnace and the following heat cycle is applied:

-   -   Increase from 20° C. to 1600° C. at 100° C./h     -   Stationary phase of 50 hours at 1600° C.     -   Decrease at 100° C./h.

After heat treatment, the deformation F of the small bar is determined using a ruler, according to FIG. 2. The smaller the deformation of the small bar, the higher the creep resistance.

The method used to determine the amount of grains of equivalent diameter greater than 1 mm in a sintered product according to the invention is the following: three samples of said sintered product are taken randomly. Each sample is then coated with a resin, for example an epoxy resin, and then polished. Each polishing is then immersed for one minute in a solution of hydrofluoric acid at 10% by weight at ambient temperature so as to reveal the grain boundaries. Each polishing is then rinsed with water and then dried. Images of the polished area are taken using an optical microscope, each image making it possible to observe at least one area equal to 8 mm by 5 mm. The area of the images taken that is occupied by grains having an equivalent diameter greater than 1 mm may be evaluated using image processing software, for instance ImageJ.

The particle size distribution of the powders was determined using a laser particle size analyzer for the particles having a size less than 2 mm and by sieving using sieves with square meshes having an opening greater than 2 mm for the particles having a size greater than 2 mm.

The apparent density and the open porosity were measured according to standard ISO5017.

The following raw materials were used for the examples:

-   -   mullite powders such that D_(99.5)<3 mm,     -   a powder of fumed silica consisting essentially of vitreous         silica microspheres such that D₉₀<4 μm, with D₅₀=0.5 μm. It has         a B.E.T. specific surface area of 14 m²/g, a silica weight         content of 93.5%, an Al₂O₃ content of 3.5% and a content of         ZrO₂+HfO₂ of 2.4%;     -   an alumina powder having an alumina content greater than 99.75%         and a D₅₀ equal to 5 μm;     -   the following forming additives:         -   a clay containing 40% of alumina,         -   a calcium lignosulfate,         -   a water-soluble nonionic cellulose ether.

The boron compound used is:

for examples 2 and 5 to 8, a powder of boron carbide B₄O having a median diameter D₅₀ equal to 4.6 μm, for example 3, a powder of boron oxide B₂O₃, sold by the company Borax, for example 4, a powder of boric acid H₃BO₃, sold by the company Borax under the name Optibor® TG, having an H₃BO₃ content greater than 99.9%.

The silica, alumina and mullite powders are mixed with 1% of clay, as weight percentage on the basis of the particulate mixture. The boron compound, the calcium lignosulfate and the cellulose ether diluted in the water required for the forming are then introduced. The amount of water is equal to 2.8% and the total amount of additive, including clay, is equal to 1.7%, as percentages on the basis of the particulate mixture.

The wet mixture obtained is then pressed in the form of bricks having the dimensions 230×114×64 mm³ on a single-acting mechanical press at a pressure of 720 kg/cm².

The bricks obtained are oven-dried for 24 hours at 110° C.

These bricks were then sintered at a stationary-phase temperature of 1700° C., the duration of the stationary phase being 5 hours, the temperature increase rate being 50° C./h. After the temperature stationary phase, the temperature is decreased, the temperature decrease rate being 50° C./h, down to 800° C., the temperature decrease then being free down to ambient temperature.

Table 1 below summarizes the tests and the results obtained, the percentages being weight percentages unless indicated.

TABLE 1 Example 1* 2 3 4 5 6 7 8 Particulate mixture Nature of the coarse particles mullite mullite mullite mullite mullite mullite mullite mullite Amount of coarse particles on the basis of 70.3 70.3 69.9 69.4 70.1 69.9 69.4 68.5 the weight of the particulate mixture (%) Amount of coarse particles of size > 1 mm, on the 39 39 39 39 39 39 39 41 basis of the weight of the particulate mixture (%) silica, silica, silica, silica, silica, silica, silica, silica, alumina, alumina, alumina, alumina, alumina, alumina, alumina, alumina, Nature of the matrix particles mullite mullite, mullite, mullite, mullite, mullite, mullite, mullite, boron boron boron boron boron boron boron compound compound compound compound compound compound compound Al₂O₃ (%) 75.47 75.28 75.10 75.05 74.91 74.54 73.62 71.82 SiO₂ (%) 23.97 23.90 23.85 23.83 23.78 23.67 23.37 22.80 ZrO₂ (%) 0.18 0.18 0.18 0.18 0.18 0.17 0.17 0.17 B₂O₃ (%) — 0.25 0.50 0.56 0.75 1.24 2.46 4.85 Other oxides (%) 0.38 0.39 0.37 0.38 0.38 0.38 0.38 0.36 Al₂O₃ + SiO₂ + ZrO₂ (%) 99.62 99.36 99.13 99.06 98.87 98.38 97.16 94.79 SiO2 + ZrO2 (%) 24.15 24.08 24.03 24.01 23.96 23.84 23.54 22.97 Al₂O₃ as weight % on the 76.12 75.48 74.86 74.69 74.23 73.02 70.15 65.02 basis of the oxides of the matrix fraction Al₂O₃ + SiO₂ + ZrO₂ 99.43 98.59 97.78 97.55 96.95 95.37 91.62 84.93 as weight % on the basis of the oxides of the matrix fraction Silica content in the matrix fraction, as weight % 22.68 22.49 22.31 22.25 22.12 21.76 20.90 19.37 on the basis of the oxide phases of the matrix fraction Alumina/silica in the matrix fraction 3.36 3.36 3.36 3.36 3.36 3.36 3.36 3.36 Nature of the boron compound — B₄C B₂O₃ H₃BO₃ B₄C B₄C B₄C B₄C Amount of boron compound (%) — 0.1 0.5 1 0.3 0.5 1 2 Sintered product Al₂O₃ (%) 75.79 75.28 75.87 75.11 75.04 74.88 74.9 74.54 SiO₂ (%) 23.57 23.47 23.23 24.05 23.54 23.53 23.59 23.58 Al₂O₃ + SiO₂ (%) 99.36 98.75 99.1 99.16 98.58 98.41 98.49 98.12 B₂O₃ (%) 0 0.13 0.24 0.19 0.26 0.65 0.71 1.41 Others (%) 0.64 1.12 0.66 0.65 1.16 0.94 0.8 0.47 Grains having an equivalent diameter > 1 mm, 36 38 35 37 35 40 37 34 as surface percentage Apparent density (g/cm³) 2.69 2.66 2.65 2.65 2.71 2.69 2.69 2.69 Open porosity (%) 13.5 14.2 14.2 13.7 11.8 12.7 12 9.9 Deformation F after creep test (mm) 4.68 1.67 1.84 1.27 1.02 0.22 0.61 1.57

It is considered that a product exhibits a considerable improvement in its creep resistance when it exhibits, with the test used, a deformation F measured after test of less than 4 mm, that is to say an improvement of at least 15% compared with the product of example 1 outside of the invention, normally used in a glass furnace crown.

A comparison of example 1 outside the invention and of examples 2 to 8 according to the invention shows the effectiveness of the addition of a boron compound on the improvement in the creep resistance.

A comparison of examples 2 to 8 according to the invention further shows that:

-   -   the creep resistance (which corresponds to a minimal measured         deformation F) is at a maximum for boron contents in the         particulate mixture such that 0.75%≦B₂O₃≦2.46%,     -   a boron content in the particulate mixture equal to 4.85% makes         it possible to improve the creep resistance of the sintered         product, but to a lesser extent.

The particulate mixture according to example 6 is the preferred example.

The sintered product obtained from the particulate mixture of example 6 is the preferred sintered product.

As clearly presently emerges, the invention provides a refractory product which has an excellent creep resistance at high temperature, and also resistance to corrosion, resistance to heat cycling and mechanical strength which make it perfectly suitable for the intended application.

Of course, the invention is not limited to the embodiments described, provided by way of nonlimiting illustration. 

1. An unshaped product comprising a particulate mixture consisting of: a coarse fraction, representing more than 50% and less than 91% of the particulate mixture, as weight percentage, and consisting of the particles having a size greater than or equal to 50 μm, referred to as “coarse particles”, and a matrix fraction, forming the remainder up to 100% of the particulate mixture, and consisting of the particles having a size less than 50 μm, referred to as “matrix particles”, the product having a chemical analysis, as weight percentage on the basis of the oxides of the product, such that: 45%<Al₂O₃, 7.5%<SiO₂<35% and 0%≦ZrO₂<33%, provided that 10%<SiO₂+ZrO₂<54%, 0.15%<B₂O₃<8%, other oxides: <6%, Al₂O₃ constituting the remainder up to 100%, said coarse fraction comprising more than 15% of coarse particles having a size greater than 1 mm, as weight percentage on the basis of the particulate mixture, said matrix fraction having a chemical analysis, as weight percentage on the basis of the oxides of the matrix fraction, such that: Al₂O₃+SiO₂+ZrO₂>86%, provided that 35%<Al₂O₃.
 2. The unshaped product as claimed in claim 1, wherein 0.2%<B₂O₃<6.5% and/or the content of other oxides is less than 5%.
 3. The unshaped product as claimed in claim 2, wherein 0.75%<B₂O₃<4.5% and/or the content of other oxides is less than 2%.
 4. The unshaped product as claimed in claim 3, wherein B₂O₃<2.6%.
 5. The unshaped product as claimed in claim 1, wherein the boron is provided by a boron compound chosen from boron carbide, boron oxides, boric acid, colemanite, sodium borate, compounds comprising silica and boron oxide, SiB₆, alumina borates, AlB₃ and mixtures thereof.
 6. The unshaped product as claimed in claim 1, wherein the matrix fraction, other than particles comprising boron, consists, for more than 80% of its weight, of alumina particles and/or silica particles and/or mullite particles and/or mullite-zirconia particles and/or particles of a silicoaluminous material having an alumina content greater than 50%.
 7. The unshaped product as claimed in claim 1, wherein more than 50% of the particles comprising boron are matrix particles, as weight percentage on the basis of the oxides.
 8. The unshaped product as claimed in claim 1, wherein Al₂O₃+SiO₂>83% or Al₂O₃+SiO₂+ZrO₂>92% or 15%<SiO₂+ZrO₂<50% or SiO₂>10%.
 9. The unshaped product as claimed in claim 8, wherein Al₂O₃+SiO₂>90% or 20%<SiO₂+ZrO₂<40% or SiO₂>13%.
 10. The unshaped product as claimed in claim 1, wherein, if the silica content in the matrix fraction is greater than 10%, as weight percentage on the basis of the oxide phases of the matrix fraction, said matrix fraction has an alumina/silica ratio greater than 2 and less than
 10. 11. The unshaped product as claimed in claim 10, wherein said ratio is less than
 5. 12. The unshaped product as claimed in claim 1, wherein more than 80% by weight of the coarse particles have a size greater than 200 μm and less than 25 mm.
 13. The unshaped product as claimed in claim 1, wherein the coarse fraction consists, for more than 80% of its weight, of alumina particles and/or mullite particles and/or mullite-zirconia particles and/or particles of a silicoaluminous material having an alumina content greater than 50%.
 14. The unshaped product as claimed in claim 1, having a chemical analysis such that: Al₂O₃: remainder up to 100%, (21%≦SiO₂≦25% and ZrO₂<1%) or (14%<SiO₂<17% and 26%<ZrO₂<32%), 0.2%<B₂O₃<2.6%, other oxides: <3%, and a matrix fraction having a chemical analysis such that Al₂O₃+SiO₂+ZrO₂+B₂O₃>90%, and an amount of matrix particles between 20% and 35% of the weight of the particulate mixture, and more than 15% of coarse particles having a size greater than 1 mm, the contents of the chemical analysis being expressed as weight percentages on the basis of the oxides.
 15. A sintered product having a microstructure consisting of grains bonded by a matrix, and having a chemical analysis such that, as weight percentages on the basis of the oxides and for a total of 100%: 45%<Al₂O₃, 7.5%<SiO₂<37% and 0%≦ZrO₂<35%, provided that 10%<SiO₂+ZrO₂<54.3%, 0.1%<B₂O₃<2.5%, other oxides: <6.4%, Al₂O₃ constituting the remainder up to 100%, the boron being distributed in the body of said sintered product, and more than 15% of grains having an equivalent diameter greater than 1 mm.
 16. The sintered product as claimed in claim 15, wherein 0.25%<B₂O₃<1%.
 17. The sintered product as claimed in claim 15, wherein the boron is distributed in the matrix substantially homogeneously.
 18. The sintered product as claimed in claim 15, wherein the aggregate consists, for more than 80% by number, of alumina grains and/or mullite grains and/or mullite-zirconia grains.
 19. The sintered product as claimed in claim 15, wherein 20%<SiO₂+ZrO₂<40%.
 20. The sintered product as claimed in claim 15, wherein Al₂O₃<85%.
 21. The sintered product as claimed in claim 15, having: a chemical analysis such that: Al₂O₃: remainder up to 100%, (21%≦SiO₂≦25% and ZrO₂<1%) or (14%<SiO₂<17% and 26%<ZrO₂<32%), 0.25%<B₂O₃<1%, other oxides: <3%, and more than 15% of grains having an equivalent diameter greater than 1 mm, the contents of the chemical analysis being expressed as weight percentages on the basis of the oxides.
 22. A glass furnace comprising a sintered product as claimed in claim
 15. 23. The glass furnace as claimed in claim 22, wherein said sintered product is in a region which is not capable of coming into contact with molten glass.
 24. The glass furnace as claimed in claim 23, wherein said sintered product is in a superstructure of said furnace.
 25. The glass furnace as claimed in claim 24, wherein said sintered product is in a crown of said furnace. 